Gasoline composition containing vanadium salts of phosphorus compounds

ABSTRACT

A GASOLINE COMPOSITION CONSISTING ESSENTIALLY OF A HYDROCARBON GASOLINE, AN ANTI-KNOCK QUANTITY OF A TETRALOWER-ALKYL LEAD COMPOUND, AND A GASOLINE-SOLUBLE VANADIUM OR CHROMIUM SALT OF A PHOSPHORUS COMPOUND HAVING THE FORMULA   R-O-P(=O)(-O-R&#39;&#39;)-OH OR R&#39;&#39;-O-P(=S)(-O-R)-SH   WHEREIN R IS A HYDROCARBON RADICAL OF UP TO 30 CARBON ATOMS, R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTILNG OF HYDROGEN AND R, S IS SULFUR AND O IS OXYGEN. THE AMOUNT OF METAL SALT ADDED IS SUFFICIENT TO PROVIDE ABOUT 0.002 TO 0.8 MILLIGRAM ATOMS, PREFERABLY ABOUT 0.025 TO 0.3 MILLIGRAM ATOMS, OF THE SELECTED METAL PER GALLON OF GASOLINE. A GASOLINE SOLUBLE NON-METALLIC AUXILIARY PHOSPHORUS COMPOUND CAN BE ADDED TO THE COMPOSITION TO PROVIDE ADDITIONAL BENEFICIAL EFFECTS.

United States Paten 3,608,232 GASOLINE COMPOSITION CONTAINING VANA- DIUMSALTS F PHOSPHORUS COMPOUNDS Frederick L. Voelz, Orland Park, and WalterF. Schoen, South Holland, Ill., assignors to Atlantic Richfield Company,New York, N.Y.

N0 Drawing. Continuation-impart of applications Ser. No. 427,078, Jan.21, 1965, and Ser. Nos. 470,598 and 470,628, both July 8, 1965, saidapplication Ser. No. 427,078 being a continuation-in-part of applicationSer. No. 306,273, Sept. 3, 1963. This application Apr. 23, 1968, Ser.No. 723,580 Int. Cl. C011 1/26 US. C]. 44-69 22 Claims ABSTRACT OF THEDISCLOSURE A gasoline composition consisting essentially of ahydrocarbon gasoline, an anti-knock quantity of a tetralower-alkyl leadcompound, and a gasoline-soluble vanadium or chromium salt of aphosphorus compound having the formula RO OH RO\ /SH RO/ \O RO \Swherein R is a hydrocarbon radical of up to 30 carbon atoms, R isselected from the group consisting of hydrogen and R, S is sulfur and Ois oxygen. The amount of metal salt added is sufiicient to provide about0.002 to 0.8 milligram atoms, preferably about 0.025 to 0.3 milligramatoms, of the selected metal per gallon of gasoline. A gasoline solublenon-metallic auxiliary phosphorus compound can be added to thecomposition to provide additional beneficial effects.

This application is a continuation-in-part of applications Ser. No.427,078, filed Jan. 21, 1965, now abandoned, Ser. No. 470,598, filedJuly 8, 1665 now abandoned, and Ser. No. 470,628, filed July 8, 1965 nowabandoned. Application Ser. No. 427,078 is a continuation-in-part ofapplication Ser. No. 306,273, filed Sept. 3, 1963, now abandoned.

The present invention relates to distillate hydrocarbon fuelcompositions which when employed in spark ignition engines lead toimprovements especially with respect to rumble. The compositions alsoexhibit other desirable characteristics such as increasedanti-corrosive, anti-preignition and anti-stalling properties. Somecompositions of the invention improve octane requirement increase whenused in spark ignition engines.

In order to improve the efficiency and increase the horsepower ratingsof gasoline engines, engine manufacturers have significantly increasedcompression ratios during the past decade. In 1952, for example, nomajor US. automobile manufacturer made a stock engine having acompression ratio as high as 8.0/1. Today engines having compressionratios greater than 10.0/ 1 are common. These high compression ratioengines have revealed a relatively new type of abnormal combustioncalled rumble. In fact, rumble is one of the major factors restrictingcompression ratios at the current levels. The rumble phenomenon is theresult of deposit induced ignition which creates abnormal pressure risesin the combustion chambers, thereby causing flexing of the crankshaft.The flexing crankshaft manifests itself by loud unnatural or shudderingengine noises.

Another disadvantage attending the use of known additives to lessenabnormal combustion of gasoline in, for instance, automobile engines, isthat they adversely affect the nature and increase the amount ofdeposits within the combustion space. These effects take on greaterimportance in the case of the higher compression ratio engines. A fuelhaving an octane number appropriate to the designed engine compressionratio is therefore unable to give the same anti-knock performance afterthe formation of such extensive deposits. To obtain the intendedautiknock performance requires a fuel of higher octane number; and thiseffect has become known as the octane requirement increase" or Ori ofthe engine.

Various commonly employed gasoline additives as, for example, phosphatecompounds such as tricresyl phosphate, cresyl diphenyl phosphate, etc.,although known to improve engine operation with respect to preignition,rumble, wild ping, autoignition and spark plug fouling, have nodecreasing effect on octane number requirement increase and many evenhave an adverse effect. Also to combat rumble effectively, relativelylarge amounts of the additives may be needed.

It has now been found that leaded gasolines having added thereto a smallamount of a gasoline-soluble chromium or vanadium salt of certainphosphorus and thiophosphorus compounds provides a composition whichimproves rumble. Further improvements in terms of octane requirementincrease and in some cases rumble are afforded by also including in thegasoline composition a nickel or cobalt salt of the phosphorus compoundsof the invention. Thus in a preferred form the gasoline includes apartial ester salt of a metal having an atomic number from 23 to 24 anda partial ester salt of a metal having an atomic number from 27 to 28,especially a combination of such chromium and nickel salts. Thecompositions of the invention also exhibit anti-rustingvanti-preignition and anti-stalling or carburetor deicing properties.The nickel and chromium salts are further advantageous in that they areespecially resistant towards deposit formation when gasoline containingthem is stored over water.

While the present invention is directed to the use of the phosphoruscompounds in gasolines compositions which contain a lead anti-knockcompound to reduce rumble and/or other adverse effects created by theaddition of the lead compound the additives can also be advantageouslyemployed in metal octane-improving additivefree, e.g. non-leadedgasolines to, for example aid in rust preventing, reducing preignitionand anti-stalling or carburetor deicing.

The phosphorus compounds, from which metal salts of the invention aremade, have the following formulae:

wherein R is a hydrocarbon radical of up to about 30 or more carbonatoms on the average, often at least about 5 and preferably about 8 to18 carbon atoms, S is sulfur, R is hydrogen or R, and O is oxygen. R canbe an aliphatic, aromatic or mixed aliphatic-aromatic radical and ispreferably non-olefinic and non-acetylenic, i.e. having adjacent carbonatoms no closer than 1.40 angstroms. The total number of carbon atoms ina molecule of the phosphorus compound is preferably up to about 30 oreven up to about 40 and the chromium or vanadium salt of the phosphoruscompound is soluble in gasoline at least to the extent employed in thisinvention.

The phosphorus compounds from which the metal salts of the invention aremade can be obtained by methods known to the art as, for instance, byreacting aliphatic alcohols, including cycloaliphatic alcohols, oraromatic hydroxy compounds With P 0 to form the phosphoric acid esters(I) and with P 8 to form the dithiophosphoric acid esters (II). Thepreferred alcohols are alkanols which can be straight or branch chainedand alkyl-substituted phenols Whose alkyl substituents contain a totalof up to 18 carbon atoms, and preferably are lower alkyl, especiallymethyl. The aromatic hydroxy compounds and aliphatic alcohols may besubstituted with non-deleterious groups. Illustrative of suitablealcohols are pentanol, butanol, octanol, isooctanol, Z-ethyl-heptanol,dodecanol, oleyl alcohol, octadecyl alcohol, tetradecyl alcohol,alcohols prepared by the x0 process, phenol and alkylated phenols suchas cresol, xylenol, propyl phenol, butyl phenol, dibutyl phenol,monoamylphenol, diamyl phenol, decyl phenol, dodecyl phenol, tetradecylphenol, hexadecyl phenol and octadecyl phenol.

The reaction of the alcohol and P 0 or P 5 to prepare the partial esterscan be conducted by heating the reactants at temperatures of from about75 C. to about 125 C. for a period of time sufiicient to effectsubstantially complete reaction, usually about 1 to 15 hours. An inertsolvent such as toluene, xylene or the like may be used to facilitatethe reaction. Suitable molar ratios of alcohol to P 05 and P S may beabout 3:1, and 4:1 respectively.

The ester products of phosphoric acid (I) thus produced, can be, forinstance, monoalkyl, dialkyl, mono aryl or diaryl esters or anycombination thereof. The mixed esters are often present, for instance,in a mole ratio of at least about 25% of each, say about 60 to 40%monoester: 40 to 60% diester. The metal salts of the esters can beprepared by directly reacting the esters with the metal carbonate oracetate. Either the metal or the acidic component of the salts may beused in excess and either the monoor dipartial ester salts may beemployed but they are conveniently prepared and made available as themixed ester salts. Mixed chromium and vanadium phosphate may also beemployed.

The diester products of dithiophosphoric acid (II) thus produced can be,for instance, dialkyl or diary] esters or any combination thereof. Themetal salts of the esters can be prepared by directly reacting theesters with the metal carbonate or acetate and either the metal or theacidic component of the salts may be used in excess.

In order to provide leaded gasolines of further enhancedcharacteristics, for instance, as to preignition, spark plug fouling andeven, in at least some cases, rumble, there can be included in thegasoline composition of the invention a gasoline-soluble phosphoruscompound having the formula:

RO OR wherein R has the value described above with respect to thephosphorus compounds from which the chromium and vanadium salts of theinvention are made; R is hydrogen or R and n is an integer of 0 or 1. Ris preferably an aromatic, e.g. phenyl, hydrocarbon radical of 6 to 12carbon atoms and can be substituted, for instance, With lower alkylgroups say of l to 4 carbon atoms. Thus, the phosphorus compound can bea mono-, di-, or triester, or a mixture of such and is preferably atriester. It is also preferred to employ a phenyl, alkyl phenyl or amixed phenyl-alkyl phenyl ester of phosphorus. Thus, one or more of theester groups is preferably an alkyl phenyl radical, often of about 7 to15 carbon atoms. See U.S. Pat. No. 2,889,212 for a further list of theuseful phosphates and phosphites.

These auxiliary phosphate and phosphite additives can be prepared byreacting the appropriate alcohol or aromatic hydroxy compound withphosphoric acid to make the phosphate or with phosphorus trichloride toform the phosphite. Illustrative of suitable alcohols and aromatichydroxy compounds are those mentioned above in the description of thephosphorous esters used to form the metal salts of the invention.Examples of suitable alkyl phenols are crtho, m a and para a eso g andxylenol; 2,4-dimethyl-6-tertiary butylphenol; octyl and nonyl phenols,etc.

By the term leaded gasoline to which the additives of the presentinvention are incorporated is meant hydrocarbon fractions boilingprimarily in the gasoline range, usually about 100 to 425 F., havingadded thereto a small amount, generally between about 1 to 6 cc. pergallon, of a tetra-loWer-alkyl lead compound as an antiknock agent. Thegasolines are usually composed of a major amount of a blend ofhydrocarbon mineral oil fractions boiling primarily in theaforementioned range and will contain varying proportions of parafiins,olefins, naphthenes and aromatics derived by distillation, cracking andother refining and chemical conversion processes practiced upon crudeoil fractions. Straight run gasolines, gasolines derived from crackinggas oil, gasolines or reformate from reforming straight run naphtha overa platinum-alumina catalyst in the presence of hydrogen, etc., arecomponents frequently used in making up a gasoline composition. Atypical premium gasoline, besides containing a small amount of ate-tra-loWer-alkyl lead compound as an anti-knock agent may also containsmall amounts of other non-hydrocarbon constituents used to impartvarious properties to the gasoline in its use in internal combustionengines, e.g. halohydrocarbon scavengers, oxidation inhibitors, etc.Such gasolines frequently have a Research Method octane number of about90 to 105, and a Motor Method octane number of about to 98.

The ester salts of chromium and vanadium are incorporated in the leadedgasoline in minor amounts sulficient to provide a composition exhibitingimproved rumble characteristics while the nickel and cobalt salts areused in minor amounts sufiicient to afford a decrease in octane numberrequirement increase. The actual amount of each additive employed willvary depending upon the particular gasoline employed, its lead contents,etc. In any event the metal salt is employed to supply 0.002 to 0.4 oreven 0.8, preferably 0.025 to 0.3 millimole or milligram atoms of themetal chromium and/ or vanadium per gallon of gasoline. The additivewill usually provide the gasoline with 0.00004 to 0.008, preferably0.0005 to 0.006 gram of metal per gram of lead. This often means thatabout 0.5 to 15 or 20 more of the chromium or vanadium salts to themetal salt ester, preferably about 4 to 10 pounds, per 1000 barrels ofgasoline is added. The cobalt or nickel salt when used is also generallypresent in an amount of about 0.002 to 0.8 millimole of metal per gallonof gasoline. A combination of the chromium or vanadium salts and thecobalt or nickel salt is advantageously in the range of about 0.002 to0.8 milligram atoms or millimoles per gallon of gasoline.

When used, about 0.05 to 0:6 theory, preferably about 0.15 to 0.5theory, of the auxiliary phosphate or phosphite additive, based on thelead content of the gasoline, are employed. The term theory as appliedto the amount of the second phosphorus additive means the amountrequired to react stoiehiometrically with the lead so that all of thelead atoms and all of the phosphorus atoms form Pb3(PO4)2.

The following examples are given to illustrate the advantages providedleaded gasolines by the additives of the present invention.

EXAMPLE I One mole of mixed, approximately 50% monoand approximately 50% di-, C -0x0 alcohol esters of phosphoric acid was reacted withslightly more than one mole of chromium acetate in a hexane solvent. Thereaction was carried out at C. for one hour, and the product was thenfiltered. The hydrocarbon solubles were Water- Washed several times,refiltered and the resulting chromium salt of mixed monoand di-C oxoesters of phosphoric acid was dried to constant weight, analyzing L827?chromium and 6.86 phosphorus.

The corresponding vanadium salt was made in a similar manner usingvanadium pentoxide. Analysis pentox ide. Analysis of the product showed1.55% vanadium and 6.41 phosphorus.

EXAMPLE H Two moles of mixed, approximately 50% mono and approximately50% di, C -x0 alcohol esters of phosphoric acid were reacted withslightly more than two moles of cobaltous carbonate in a hexane solvent.The reaction was carried out at 75 C. for one hour, and the product wasthen filtered. The hydrocarbon solubles were water-washed several times,refiltered and the resulting cobalt salt of mixed monoand di-C oxoesters of phosphoric acid was dried to constant weight, cobalt 4.53% andphosphorus 4.50%.

The corresponding nickel salt was made in a similar manner using nickelcarbonate, with the reaction being conducted at 80 to 90 C. Analysis ofthe product showed 6.52% nickel and 6.35% phosphorus.

EXAMPLE III A sample of a base gasoline was obtained which was composedof 25 volume percent straight run gasoline, 25 volume percentbutane-butylene alkylate and 25 volume percent reformed naphtha. Thebase gasoline analyzed 6% olefins and 20% aromatics and contained 3 cc.per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyllead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9%hydrocarbon diluent, dyes, etc.). The base gasoline containing thetetra-ethyl lead had an API gravity of 61.2, an octane number of 100 bythe Research Method and an octane number of 92 by the Motor Method. TheASTM distillation of the gasoline was as follows:

IBP 93 Into the separate portions of the leaded gasoline are addedeither the chromium salt of Example -I in a concentration that provides25 lbs. of the ester salt per 1000 barrels of the leaded gasoline or thevanadium salt of Example I in a concentration that provides 25 lbs. ofthe ester salt per 1000 barrels of the leaded gasoline. The gasolinealso contained 0.2 theory of cresyl diphenyl phosphate, about 2.5 poundsof phenylenediamine, an oxidation inhibitor, per 1000 barrels ofgasoline and a commercial amine salt of a phosphoric acid estercorrosion inhibitor.

The above gasoline with the metal phosphate ester additives is evaluatedin a 1962 Chevrolet V-8, 327 cubic inch, 10.2:1 compression ratio engineto obtain the equilibrium rumble requirement (LIB). LIB number is ameasure of the rumble tendency of an engine after a given time of use.The number represents the percent isooctane [containing 3 cc./ gal. TEL]required in a blend with benzene [containing 3 cc./gal. TEL] after agiven period of engine operation using the fuel under test, to avoidrumble at a given r.p.m., e.g. 2000 rpm. The test procedure comprisesstopping the gasoline to the engine at any given period of engineoperation and employing as a fuel to the engine containing a certainpercent of isooctane in an isooctane-benzene blend (containing 3 cc.T-EL/gal.), manually opening the throttle at a given rate and recordingthe rpm. at which rumble occurs, if any in fact occurs. The faster youare able to run the engine with the lowest percent of isooctane in theblend the better the rumble resistance of the engine. Thus, the lowerthe LIB number the better the rumble characteristics of the engine.

The above fuel without the chromium or vanadium salt, gave in thisengine an equilibrium rumble requirement of 70 LIB. After the engine wascleaned, the same fuel without the amine phosphate corrosion inhibitorbut containing 25 pounds of the chromium salt of Example I per 1000barrels, when used in the engine gave an LIB number of only 10. In asimilar test with the same fuel but containing 25 pounds of the vanadiumsalt of Example I per 1000 barrels instead of the chromium salt, the LIBrating is also significantly reduced.

EXAMPLE IV The chromium and vanadium salts of Example I were added, inthe amount of 2 pounds per 1000 barrels, to a gasoline containing 37volume percent light straight run gasoline, 23 volume percent lightcatalytically cracked gasoline, 13 volume percent heavy catalyticallyreformed gasoline and 27 volume percent heavy catalytically crackedgasoline. In a 4-hour accelerated rust test the base gasoline gave apoor or E rating but after addition of the chromium salt a rust ratingof B+ was obtained and after addition of the vanadium salt to the basegasoline a rating of B was obtained. In testing these salts the gasolinealso contained 3 cos. TEL/gaL, 0.2 theory of cresyl diphenyl phosphate,0.15 volume percent methanol and a metal deactivator, 1 lb./1000barrels. The corrosion test involved placing a steel specimen in contactwith agitated gasoline and water at 100 F. for about four hours and thespecimen is inspected to ascertain the extent of rust according toratings A to E, see US. Pat. No. 2,966,458.

EXAMPLE V A composition of superior rumble and octane requirementincrease characteristics is the final chromium saltcontaining gasolineof Example III also having in addition 20 lbs. per 1000 barrels of thenickel salt of Example II.

EXAMPLE VI Also included in the gasoline were phenylene diamineoxidation inhibitor and 3.0 cc. of tetraethyl lead admixed with anethylene dichloride scavenger.

The table below reports data as wild ping counts per hour obtained inpreignition tests using the above gasoline containing the chromium saltadditive of Example I and from 0 to 0.3 theory of cresyl diphenylphosphate (CDP).

Chromium salt, N0./1,000 bbls. gasoline GDP, theories 0 These dataestablish the elficiency of the chromium salt in combating surfaceignition in the presence or absence of cresyl diphenyl phosphate.

EXAMPLE VII One mole of dithiodiisodecyl phosphoric acid ester isreacted with slightly more than one mole of chromium acetate in a hexanesolvent. The reaction is carried out at C., for one hour, and theproduct is then filtered. The hydrocarbon solubles are water-washedseveral times,

refiltered and the resulting chromium salt of thedithiodiisodecylphosphoric acid ester is dried to constant weight. Thesalt contains a calculated metal content of 6.4% by weight chromium.

The corresponding vanadium salt calculated at 4.0% by weight V, is madein a similar manner using vanadium pentoxide.

EXAMPLE VIII Two moles fo dithiodiisodecylphosphoric acid ester arereacted with slightly more than two moles of cobaltous carbonate in ahexane solvent. The reaction is carried out at 75 C., for one hour, andthe product is then filtered. The hydrocarbon solubles are water-washedseveral times, refiltered and the resulting cobalt salt of thedithiodiisodecylphosphoric acid ester is dried. The calculated cobaltcontent of the product is 6.7% by weight.

The corresponding nickel salt, calculated at 6.6% by Weight nickel, ismade in a similar manner using nickel carbonate, with the reaction beingconducted at 80 to 90 C.

EXAMPLE IX A sample of a base gasoline is obtained which is composed of25 volume percent straight run gasoline, 25 volume percent lightcatalytically cracked gasoline, 25 volume percent butane-butylenealkylate and 25 volume percent reformed naphtha. The base gasolineanalyzes 6% olefins and 20% aromatics and contains 3 cc., per gallon ofTEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0%ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbondiluent, dyes etc.) The base gasoline containing the tetraethyl lead hasan API gravity of 61.2, an octane number of 100 by the Research Methodand an octane number of 92 by the Motor Method. The ASTM distillation ofthe gasoline is as follows:

F. IBP 93 122 50% 201 90% 338 Into separate portions of the leadedgasoline are added either the chromium salt of Example VII in aconcentration that provides 25 lbs., of the ester salt per 1000 barrelsof the leaded gasoline or the vanadium salt of Example VII in aconcentration that provides 25 lbs., of the leaded gasoline. Thegasoline also contains 0.2 theory of cresyl diphenyl phosphate, about2.5 pounds of phenylenediamine, an oxidation inhibitor, per 1000 barrelsof gasoline and a commercial amine salt of a phosphoric acid estercorrosion inhibitor.

The above gasoline compositions when evaluated in a 1962. Chevrolet V-8,327 cubic inch, 10.2:1 compression ratio engine exhibited an improvedequilibrium rumble requirement (LIB).

EXAMPLE X The chromium and vanadium salts of Example VII when added, inthe amount of 2 pounds per 1000 barrels to a leaded (3 cc. TEL as MotorMix) gasoline composed of 37 volume percent light straight run gasoline,23 volume percent light catalytically cracked gasoline, 13 volumepercent heavy catalytically reformed gasoline and 27 volume percentheavy catalytically cracked gasoline, provides a composition of enhancedrust resistance.

EXAMPLE XI Compositions of superior rumble and octane requirementincrease characteristics are the final chromium saltcontaining gasolinesof Example IX also having in addition 20 lbs. per 1000 barrels of thenickel salt of Example VIII.

EXAMPLE XII A leaded (3 cc. TEL as Motor Mix gasoline composed of 14volume percent straight run gasoline, 32.7 volume O\ /SH RO \S ROwherein R is a hydrocarbon radical of up to 30 carbon atoms, and R isselected from the group consisting of hydrogen and R and the amount ofsaid vanadium salt being 0.002 to 0.8 milligram atoms of metal pergallon of gasoline.

2. The composition of claim 1 in which there is also included about 0.05to 0.6 theory of a gasoline-soluble phosphorous compound having theformula and wherein R is a hydrocarbon radical of up to about 30 carbonatoms on the average, R is selected from the group consisting ofhydrogen and R, and n is an integer having a value of 0 or 1.

3. The composition of claim 2 wherein at least one R in the structure ofclaim 2 is an alkyl phenyl radical of 7 to 15 carbon atoms.

4. The composition of claim 3 wherein the amount of phosphorus compoundis abuot 0.15 to 0.5 theory.

5. The composition of claim 1 wherein the vanadium salt is a salt of aphosphorus compound having the formula RO\ /OH R'O 0 wherein R is ahydrocarbon radical of from about 8 to 18 carbon atoms, and R isselected from the group consisting of hydrogen and R, the amount of saidvanadium salt being 0.025 to 0.3 milligram atoms of vanadium per gallonof gasoline.

6. The composition of claim 5 in which there is also included about 0.05to 0.6 theory of a gasoline-soluble phosphorus compound having theformula RO\ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to15 carbon atoms and R is selected from the group consisting of phenyland R.

7. The composition of claim 6 wherein the non-metallic phosphoruscompound is cresyl diphenyl phosphate.

8. The composition of claim 1 in which there is included about 0.002 to0.8 milligram atoms per gallon of said gasoline of a gasoline-solublemetal salt of a phosphorus compound having the formula R'O\ OH 2: R'O owherein R is a hydrocarbon radical of up to 30 carbon atoms and R isselected from the group consisting of hydrogen and R said metal havingan atomic number of from 27 to 28.

9. The composition of claim 8 in which there is also included about 0.05to 0.6 theory of a gasoline-soluble phosphorus compound having theformula wherein R is a hydrocarbon radical of up to about 30 carbonatoms on the average, R' is selected from the group consisting ofhydrogen and R, and n is an integer having a value of or 1.

10. The composition of claim 9 wherein at least one R in the structureof claim 9 is an alkyl phenyl radical of 7 to 15 carbon atoms.

11. The composition of claim 10 wherein the amount of prosphoruscompound is about 0.15 to 0.5 theory.

12. The composition of claim 8 wherein the metal of atomic number 27 to28 is nickel.

13. The composition of claim 1 wherein the vanadium salt is a salt of aphosphorus compound having the formula:

wherein R is an alkyl radical of 8 to 18 carbon atoms on the average,the amount of said vanadium salt being sufficient to provide 0.025 to0.3 milligram atoms of vanadium per gallon of gasoline.

14. The composition of claim 13 in which there is also included about0.05 to 0.6 theory of a gasolinesoluble phosphorus compound having theformula:

RO\ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to carbonatoms on the average, and R is selected from the group consisting ofphenyl and R.

15. The composition of claim 14 wherein the nonmetallic phosphoruscompound is cresyl diphenyl phosphate.

16. The composition of claim 1 in which there is included about 0.002 to0.8 milligram atoms of a gasolinesoluble metal salt of a phosphoruscompound having the formula:

wherein R is a hydrocarbon radical of up to 30 carbon atoms on theaverage, said metal having an atomic number of from 27 to 28.

17. The composition of claim 15 in which there is also included about 16to 195 pounds per thousand barrels of a gasoline-soluble phosphoruscompound having the formula:

R 0 OR RO/ 011 wherein R is a hydrocarbon radical of up to about 30carbon atoms on the average, R is selected from the group consisting ofhydrogen and R, and n is an integer having a value of 0 to 1.

18. The composition of claim 17 wherein at least one R in the structureof claim 23 is an alkyl phenyl radical of 7 to 15 carbon atoms.

19. The composition of claim 18 wherein the amount of phosphoruscompound is about 48 to pounds per thousand barrels of gasoline.

20. The composition of claim 16 wherein the metal of atomic number 27 to28 is nickel.

21. The composition of claim 1 wherein there is included about 0.025 to0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metalsalt of a phosphorus compound having the formula:

RO\ /SH I R0 s wherein R is an alkyl group of 8 to 18 carbon atoms onthe average, said metal having an atomic number of from 27 to 28.

22. The composition of claim 1 wherein there is included about 0.025 to0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metalsalt of a phosphorus compound having the formula:

wherein R is an alkyl group of 8 to 18 carbon atoms on the average and Ris selected from the group consisting of hydrogen and R, said metalhaving an atomic number of from 27 to 28.

References Cited UNITED STATES PATENTS 2,889,212 6/1959 Yust et al.44--69 3,445,206 5/1969 Revukas 44-69 DANIEL E. WYMAN, Primary ExaminerY. H. SMITH, Assistant Examiner US. Cl. X.R.

44--68, 78, Dig. 3, Dig. 4

UNITED STATES PATENT eFFroE CERTIFICATE OF CORRECTIGN Patent o, 3, 3Dated September 28, 1971 Inventor(5) Walter F. SChOen and Frederick L.VO1Z It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Column 1, line MO: "1665" should be -l965--.

Column 5, lines 2 and 3: Delete "Analysis pentoxide."

Column 7, line 9: "f0" should be --of--.

Column 8, Line 38: "abuot" should be -about-.

Column 10, line 1 "23" should be --17--.

Signed and sealed this 23rd day of May 1972.

(SEAL) Attest:

ROBERT GOTTSCI-ZALK EDWARD MFLETCHR, JR.

Commissioner of Patents Attesting Officer 'ORM PC4050 H0-691 USCOMM-DCbOL-U'G-Pfl r: us, sovznnmam PFHNTING OFFiCE lsus 0-356-334

